Chemical properties and reactions

Introduction
The purpose of this subject is to familiarize the trainees with the basic chemical properties of the
different cargoes and/or groups of cargoes on tankers. The instructor should start with a
description of atoms and explain the periodic system and the periodic table. A chemical reaction
and the forming of simple molecules should then be explained, using the most common
hydrocarbon molecules as examples. The difference between the molecules of saturated
hydrocarbons, unsaturated hydrocarbons and those of other common chemical compounds
should be explained.
All chemical compounds belong to a 'chemical family group'. The following 'chemical families'
should be presented and explained, as a chemical cargo will belong to one of them:
Acid (organic)

Acid (inorganic)

Alcohols

Aldehydes

Alkalis

Amines

Esters

Ethers

Glycols

Glycol ethers

Halogenated compounds

Halogens

Hydrocarbons

Ketones

Nitriles

Phenols

Chemical reaction and ways of preventing it should be explained with a view to the different
molecular structures, and references should be made to the ICS Cargo Data sheets for common
cargoes.

PROPERTIES OF HAZARDOUS MATERIALS

It is not necessary that everyone involved in the transport of dangerous goods should be a
qualified scientist. In the management of risk however, it is important to understand the nature of
the risks involved. These notes should act as a reminder of the course content designed to help
you understand the terms used in the information given in the transport codes, cargo data sheets
and emergency action advice.
Here is a list of words taken from the above sources, which the following information should
make it possible for you to understand or understand better.
REACTION

REACTIVE

EXOTHERMIC

DECOMPOSITION

POLYMERIZATION

OXIDISING AGENT

OXIDISE, OXIDATION

SPONTANEOUS COMBUSTION

ACID

ALKALINE

CORROSIVE

CAUSTIC

DILUTE

NEUTRALISE

THE HEAT PRODUCED BY REACTION OR DILUTION (SOLVATION)

CONTROL TEMPERATURE

EMERGENCY TEMPERATURE

THE EVOLUTION OF GASES

SUBLIMATION

COMBUSTION

FLASHPOINT

IGNITION TEMPERATURE

INHIBITOR

MISCIBLE

IMMISCIBLE

VOLATILE

HERMETICALLY SEALED

EXPLOSIVE

HIGH EXPLOSIVE

PROPELLANT

MEANS OF INITIATION

DETONATORS

RANGE OF FLAMMABILITY

VAPOUR DENSITY

AEROSOL

PYROPHORIC

INHALATION

INGESTION

ABSORPTION

TOXIC OR POISONOUS

INJURIOUS

NOXIOUS

HARMFUL

LIQUEFIED GAS

CRITICAL TEMPERATURE

FILLING RATIO

ULLAGE

NARCOTIC

HYGROSCOPIC

DELIQUESCENT

REFERENCE TEMPERATURE

DRY CHEMICAL

DRY AGENT

RADIOACTIVE

FISSLE

ATOMS, ELEMENTS, MOLECULES AND COMPOUNDS

There are 104 substances, the smallest particle of which is one ATOM. These substances are
called ELEMENTS. Examples of elements are iron, oxygen or sulphur. The smallest particle of
any other substance, such as wood, human flesh, plastic materials, is one MOLECULE which is
made up of atoms of the elements. For example, A hydrocarbon molecule is characterized by the
presence of carbon and hydrogen atoms in various arrangements.
HOW BIG ARE ATOMS?
Individual atoms are so small they cannot be seen even with the most powerful modern
microscope. It would take nearly a million atoms side by side to equal the thickness of one page
in a book. It is only by indirect experiment that scientists have been able to guess at their nature,
hence any reference to the structure of atoms/molecules is called "atomic or molecular theory".
SUB-ATOMIC STRUCTURE
There are three particles which make up an atom (in the simplest theory):

ELECTRONS, which are charged negatively but have no mass (weight).

PROTONS, which are charged positively and have mass.

NEUTRONS, which have no electrostatic charge but have the same mass as a proton. All the
mass of an atom is in a tiny nucleus, in the centre of the atom, which is made up of
protons and neutrons. The electrons are in shells at a certain distance from the nucleus and in the
neutral atom there are as many electrons as protons so that their charges cancel each other out.
Atoms stay away from each other and create the illusion of solidity because the outer shell of
each is negatively charged and LIKE CHARGES REPEL.

Figure 1.
The simplest atom is that of the element hydrogen, which has one electron around a nucleus
containing one proton. Helium has two protons and two neutrons in the nucleus and two
electrons in the outer shell.
The only difference in the structure of hydrogen and helium is in the number of sub-atomic
particles, and yet hydrogen is highly flammable and reactive whereas helium is INERT. What is
meant by inert is that if it is heated to 4000C or treated with the strongest acid this element
undergoes no chemical change, so it would seem that this arrangement of a pair of electrons in
nature is very stable whereas a single electron is not.
PERIODIC TABLE OF THE ELEMENTS
When all the atoms of the elements are arranged in the order of the number of particles in each
one, a periodicity is discovered. That is to say that every eighth or, later in the series, eighteenth
element has similar chemical and physical characteristics.
H

He

Hydrogen

Helium

Li

Be

Ne

Boron

Carbon

Lithium

Beryllium
Mg

Sodium

Al

Si

Magnesium Aluminium Silicon

Ca

Potassium Calcium

Ga
Gallium

Nitrogen
P

Oxygen
S

Phosphorus

Sulphur

As

Se

Ge
Germanium

Arsenic

Fluorine Neon Na
Cl

Ar

Chlorine Argon K
Br

Kr

Selenium Bromine Krypton

Figure 2. A shortened form of the Periodic Table of the Elements

As we proceed through the table from left to right each atom has its number of particles
increased by one proton, one neutron and one electron so that its relative atomic weight (weight
relative to that of carbon 12) increases by two (remember electrons have no weight). After
helium the next element, lithium, has three electrons. Two make a pair like those of helium and
the third is on its own in an outer shell. All those elements in the first column have a single
electron in an outer orbit like hydrogen, they are all metals, and they react violently with water to
make alkaline solutions. The elements in column 1 are known as the alkaline metals.
Across the row each element increases its number of electrons in its outer shell by one, Li lithium (1), Be - beryllium (2), B - boron (3), C - carbon (4), N - nitrogen (5), O - oxygen (6), F fluorine (7). All the elements in column 7 are rather nasty, poisonous and highly reactive non-

metals, they are known as the halogens. In column 8 is Ne - neon which is an inert gas, like
helium. All the elements in column 8 have eight electrons in their outer shell and are inert; so it
appears that an arrangement of eight electrons is something very stable in nature. These eight
electrons are believed to form four pairs, equally spaced around the atom.
In chemical reactions the elements react by borrowing, sharing or losing electrons until they
achieve the magic number of eight electrons in their outer shells, like the inert gases.
ISOTOPES
It is possible for some atoms to have more or less neutrons than they would normally have. They
have the same chemical properties as the parent atom, but a different atomic weight. These are
called isotopes.
RADIOACTIVITY
The isotopes of some elements are unstable and may disintegrate into the atoms of two smaller
elements releasing particles and energy. These are termed radioactive isotopes and substances
containing them are referred to as FISSILE. These particles (alpha and beta radiation) and
energy (gamma) are harmful to living tissue. Artificially produced medical and industrial radio
isotopes are not fissile.
ELECTRO-VALENT
COMPOUNDS
After neon, sodium adds one more electron in a new outer shell. Sodium is therefore an alkaline
earth metal which reacts violently with water, this reaction releases enough energy to melt the
sodium metal and perhaps ignite it. Electrons are added across this row until the inert gas, argon
is reached with its pattern of eight electrons in the outer shell. One back from this in column 7 is
chlorine with 7 electrons, a halogen, it is a poisonous green gas, a very dilute solution of which is
used to kill bacteria in water.

Figure 3. Formation of sodium chloride

If these two elements are put together and excited (given some energy), the single electron will
jump from the sodium atom to the chlorine atom, leaving the sodium with eight electrons in its
outer shell like neon, and the chlorine with a completed outer shell like argon.
However the sodium atom now has one more proton than electrons and is positively charged.
The chlorine has an extra electron and is negatively charged. These two charged atoms (called
IONS) then stick together to form one molecule of the electro-valent compound sodium chloride,
on the principle that unlike charges attract. This is the nature of chemistry, sodium chloride is
common salt, which you put on your dinner!
CO-VALENT
COMPOUNDS
Sometimes
the
pattern
of
eight
is
achieved
by
sharing
electrons.
Water is one example of this. The molecule of water is written as H2O. This is the chemist's
shorthand way of describing a molecule which contains two atoms of hydrogen and one atom of

oxygen.
In the complete molecule, each hydrogen has two electrons (like the inert gas helium) and each
oxygen is associated with eight electrons (like the inert gas neon) although no electrons have
actually passed from one atom to the other.

Figure 4. Formation of H2O

NB Co-valent compounds do not usually have a charge, but in the case of water because the
molecule is "bent" (i.e. not symmetrical), it has a very slight negative charge on the oxygen end
and a very slight positive charge on the hydrogen end. The water molecule is said to be POLAR.
SOLUBILITY
When electro-valent salts dissolve the charged ions separate and become surrounded by water
molecules, with the positive end of the polar water molecule sticking to negatively charged ions
and the negative end sticking to the positively charged ions. Polar liquids can only dissolve
electro-valent compounds. Co-valent substances will only dissolve in non-polar liquids.
For example, wax will dissolve in petrol but not in water, and salt will dissolve in water but not
petrol. Polar liquids will mix, so will non-polar, but polar and non-polar will separate, e.g. oil
and water.
Liquids which will mix are called MISCIBLE. Liquids which will separate are called
IMMISCIBLE.
If a description just says "miscible" it usually refers to miscibility with water.
TYPES OF CHEMICAL REACTION
There are only two types of basic chemical REACTION, other reactions are variations of these
or their opposites.
1. COMBINATION, such as

DECOMPOSITION is the opposite of this, if a compound can be split by heating it is

called thermal decomposition

2. REPLACEMENT reactions, such as

In the above reaction, two atoms of zinc metal (Zn) lose electrons to become zinc ions
+
+
(Zn ), the hydrogen gains an electron to go from being two hydrogen ions (H ) to being a
molecule of hydrogen gas (H2).
This is because some substances more strongly attract electrons than others. Replacement
reactions occur mostly in solutions when "free ions" are produced. This explains the
electrolytic nature of solutions of salts. Galvanic corrosion is a form of replacement
reaction with electrons flowing from one metal to the other.
If, after mixing together two different solutions, the mixture contains a pair of ions which, when
combined, form a substance which is insoluble, this substance will fall out of the solution as a
precipitate.
ACIDS (turns litmus red)
The mineral acids - hydrochloric (HCl), sulphuric (H2S04), and nitric (HNO3). The organic acids
- e.g. acetic acid (CH3COOH). The reaction outlined earlier between zinc and hydrochloric acid
is an example of the corrosion of a metal by an acid. An acid is something that produces free
hydrogen ions in solution which will then attack by replacement reactions. It is the number of
free hydrogen ions per litre in solution which denotes how strong an acid is.
This is expressed on a scale from 0 to 14, called the pH, where 0 is the strongest acid and 7 is
neutral; of course 14 is the strongest alkaline (base).

Figure 5 . The pH scale

ALKALINES (BASES) (turns litmus blue)
A substance which produces hydroxide ions (OH) in solution is called an alkali. They are
CORROSIVE only to the soft metals such as aluminium but attack animal protein to turn it into
a soapy substance. Such substances in solution are termed CAUSTIC which means 'burns human
flesh'.

NEUTRALISING REACTIONS
HCl + NaOH = NaCl + H2O An acid plus alkali gives a salt plus water.
HEAT IN REACTIONS
As in the previous examples, when a chemical reaction occurs either heat is given out, or heat is
required to keep the reaction going.
Those which produce heat are called EXOTHERMIC.
Those which require heat are called ENDOTHERMIC.
An exothermic reaction may produce enough heat to raise the heat level (temperature) of a
substance, or adjacent material, above its self ignition temperature resulting in
SPONTANEOUS COMBUSTION.

Figure 6. Energy diagram

Figure 7. Effect on energy diagram

* A catalyst in chemistry is something which helps promote a chemical reaction without
appearing in the end products.
Figure 6(a) shows that a substance liable to react exothermically may be safe to carry if a large
amount of activation energy is required to start it off. Figure 7(a) shows the effect of raising the
temperature thus raising the energy level of the reactants. This leaves a smaller amount of
required activation energy, which makes the substance less stable. Some substances are made
safe for carriage by temperature control. Figure 7(b) shows that a catalyst inadvertently allowed
to contaminate a substance may provide an alternative chemical route which does not require so
much activation energy, thus once again making the substance unstable. It may be necessary to
add an inhibitor to prevent this happening.
OXIDATION
AND
REDUCTION
When a substance combines with oxygen it is said to be OXIDISED, when oxygen is removed it
is said to be reduced. This definition has been extended to include any reaction where a metal
loses electrons (oxidation) or gains electrons (reduction).

By the extended definition chlorine is an oxidising agent,

2+

M+Cl M Cl 2 the metal (M) has lost electrons and has therefore been oxidised, chlorine is
therefore referred to as an oxidising agent.
Substances can burn in an atmosphere of chlorine.
The pre-fix per- in chemistry means that the substance named in the root word is present in a
more than usual amount so that a peroxide is a substance with an unusual amount of oxygen and
is probably a strong oxidising agent.
Hypo- means less than so we have the series
ClO hypochlorite
ClO2 chlorite
ClO3 chlorate
ClO4 perchlorate
All of which form compounds such as calcium hypochlorite or potassium chlorate which are
strong oxidising agents and have in the past been used in the manufacture of explosives.
Explosive by being able to provide oxygen to burn combustible material in an enclosed spaced,
or if it is heated in an enclosed space it may explode due to thermal decomposition.
Some of the strong mineral acids HClO4, perchloric acid, and HNO3, nitric acid, as well as being
acid can be oxidising agents.
Oxidation is exothermic; in fact combustion is the rapid oxidation of organic material.
Oxidising agents may set organic material on fire (wood, paper, cotton or organic oils)
So you can see that organic peroxides may be self reactive.
ORGANIC CHEMISTRY
This is the study of the carbon compound which is the compound most frequently found in living
(organic) things.
Carbon has four electrons in its outer shell with which it can make co-valent chemical bonds.
The simplest organic compound being methane (CH4):

Figure 8. Methane
Carbon has the unique property of being able to make bonds to another atom of the same element
(Alkanes)(C-C). They can also make double bonds (Alkenes)(C=C), and even triple bonds
(Alkynes)(CC). The significance of multiple bonds is that they are unstable and therefore more
reactive than compounds containing only single bonds.
Carbon compounds may build up into long chains (ALIPHATIC) or rings (AROMATIC).
To try to simplify this complex subject substances are often grouped into families. For instance,
those carbon compounds containing only carbon and hydrogen are referred to as hydrocarbons,
they are chemically inactive other than giving off flammable vapours.
FUNCTIONAL
GROUPS
What makes carbon compounds reactive are small groups of atoms, called functional groups,
attached to the carbon backbone. They have the property of attracting or releasing electrons to or
from the carbon chains. These electrons may then break or make chemical bonds.
Some examples are
CH3CH2CH3 propane (no functional group) may be written C-C-C This is an example of a
saturated aliphatic hydrocarbon (unreactive).
C-C=C propene This is an example of an unsaturated hydrocarbon compound (unsaturated
because further reaction can take place at the double bond).
C-C-C-OH propanol an alcohol (flammable)
H
|
C-C-C=0 propanal an aldehyde
OH
|
C-C=0 ethanoic acid (acetic acid)
Ethanoic acid instead of acetic acid is an example of a systemic name as against a trivial name.
The problem with trivial names is that they may be different in different countries, and different
in different industries in the same country. Formulae like the ones above are called skeletal
formulae and tell a chemist much more about the nature of a substance than a formula like
C3H6O. The systemic name allows a chemist to draw the skeletal formula.
If a skeletal formula does not show four chemical bonds to a carbon it should be understood that
the other bonds are taken up by hydrogen.
Skeletal formulae and systemic names are being included in the codes and datasheets and should
be used when asking for assistance or advice. Great care must be taken with spellings and also
with numbers which denote the position of functional groups on the carbon skeleton. With larger
molecules, the positioning of the functional groups may become important if it decides whether

the shape of the molecule allows two functional groups to be near enough to each other to react
when two reacting molecules come together.

Figure 9 a and b would be likely to react a and c may not.

Industry is slow to change and the systemic name is often only used for more complicate
molecules and the trivial name is still used for common substances handled in large quantities,
an example of this is that propene (see above) would most often be referred to under its trivial
name, propylene. A good chemical dictionary would list a substance's alternative names, which
may be several.
Organic chemistry is very complicated and often even a chemist can only determine the true
nature of a substance by reference to literature. Which is why getting the name exactly right is so
important.
It is the solvents, catalysts and intermediates associated with organic chemistry which cause
many of the hazards associated with the modern transport industry.
As mentioned earlier, to try to simplify organic chemistry, substances are often put in groupings
with similar characteristics mostly to denote compatabilities for transport.
Hydrocarbons are substances whose molecules contain only hydrogen and carbon atoms in
various arrangements and may be gases, liquids or solids at ambient temperatures and pressures
depending upon the number of the carbon atoms in the molecular structure.
Those hydrocarbons with up to 4 carbon atoms are gaseous at ambient conditions and comprise
the hydrocarbon liquefied gases.
Hydrocarbons with from 5 up to about 20 carbon atoms are liquid at ambient conditions.
Hydrocarbons with more carbon atoms are solid at ambient temperature
Gaseous - liquid - solid
4 20
number of carbon atoms
The carbon atom has four unpaired electrons. By making electron pairs with the electrons of one
or more other atoms, the carbon atom can bond to make organic molecules. These other atoms
can be carbon or atoms of other elements. A hydrogen atom, however, has only one electron for
bonding and can unite with only one other atom. Both the following substances have the same
formula C4H10

C-C-C-C

n-butane CH3-CH2-CH2-CH3

C-C-C
Iso-butane CH3-CH(CH3)-CH3
branched chain

straight chain (normal)

(On the skeletal formulae, mentally complete the number of chemical bonds on each carbon to
four, with hydrogen)
Iso- is short for isomer and is the name used to describe substances with the same formula but
with the atoms arranged differently. Where isomers are possible any product is most likely to be
a mixture of these isomers.
The figure above illustrates the saturated molecular structure of iso-butane (i-butane) and normal
butane (n-butane) (the systemic name for isobutane would be 2-methylpropane indicating that a
methane molecule is bonded to the second carbon atom in the propane chain). Examination of
these examples will show that, for saturated hydrocarbons, the proportion of carbon and
hydrogen atoms in the molecule will be in accordance with the general formula CnH2n+2. Thus,
methane (CH4), ethane (C2H6), and propane (C3H8) all are saturated hydrocarbons.
C-C-C-C

C-C-C-C-C

(CH3CH2CH2CH3)

(CH3CH2CH2CH3)

butane

pentane

The saturated aliphatic hydrocarbons are also known as the alkanes, and in industry as the older
name paraffins. C8 would be octane, the main constituent of petrol. They are all flammable gases
or liquids which will give flammable vapours and will burn in air and/or oxygen to produce
carbon dioxide and water vapour. As they are chemically non reactive they do not present
chemical compatibility problems with materials commonly used in handling.
Where there is less than the full complement of hydrogen atoms as given by CnH2n+2, two or
more carbon atoms must have double or perhaps triple bonds. As shown in the following
examples of unsaturated aliphatic compounds..
C-C=C CH2-CH=CH2 C=C-C=C CH2=CH-CH=CH2
propylene (propene) (C3H6) butadiene (buta-1,3-diene) (C4H6)
The unsaturated aliphatic hydrocarbons are also known as the alkenes, and in industry the older
name, olefins.

As an illustration of the above, on a liquefied gas carrier, the saturated aliphatic hydrocarbons
methane, ethane, propane and butane, are not considered to have any reactivity hazard (other
than the formation of hydrates at very low temperatures). They have no smell and a smell
(stenching) may be added for safety reasons. Even the unsaturated hydrocarbons ethylene,
propylene, butylene, butadiene and isoprene are not considered to be reactive with materials of
construction. Whereas butadiene and isoprene, each having two pairs of double bonds, are by far
the most chemically reactive within this family group. They may react with air to form peroxides
which
are
unstable
and
tend
to
induce
polymerisation.
Butadiene is incompatible in the chemical sense with copper, silver, mercury, magnesium,
aluminium and monel. Butadiene streams often contain traces of acetylene, which can react to
1
form explosive acetylides with brass and copper.
Acetelyne C2H2 (systemic name ethyne) is an example of a series called the alkynes which have
three bonds between the carbons and are even more reactive and unstable than the alkenes.

In the hydrocarbon series all that happens when an additional CH2 group is added is that physical
properties such as boiling point and vapour density increase. As the molecule gets larger and
heavier it needs more energy for the molecules to fly off the liquid surface and become free gas
molecules.
If hydrogen is replaced with a functional group (substitution) a new series starts, all containing
that functional group, of course a large molecule can contain more than one functional group
hence the complexity of organic chemistry.
Some more examples of functional groups which can form series are:
Halogens - fluorine, chlorine, bromine or iodine.
Amines -NH2
Amides -CONH2
Aldehydes -CHO
Ethers -OKetones >C=O
Esters COOCH2CH3

It is not necessary or desirable that the non-chemist should learn the properties of all possible
combinations, an incorrectly memorised detail may have fatal consequences. The data sheets for
each cargo handled should be read and the information kept ready to hand in case containment is
lost and the cargo presents a hazard. Special carriage conditions should be carefully noted.
Some general properties are given here together with the product obtained by substituting a
hydrogen for a functional group on ethane. Generally the reactivity decreases with size of the
molecule.
Alcohols - ethanol CH3CH2OH
All the alcohols are low flashpoint flammable liquids.
Most are toxic except ethanol.
Alcohols are miscible with water and fire fighting foams are destroyed by having the water
leached out of them. Special alcohol resistant foams have been developed.

Glycols - ethylene glycol CH2OHC2HOH

If two or more OH groups are substituted these higher alcohols are called glycols.
Toxic only if ingested, combustible rather than flammable.
Exothermic reactions with oxidising agents.

Acids - propionic acid (ethanoic acid) CH3CH2COOH

Organic acids are weak acids but have hazards associated with toxicity or reactivity.
Miscible with water.

Amines
Generally highly toxic by all three routes of entry - inhalation, ingestion and skin contact.
Flammable to produce ammonia and hydrogen cyanide as products of combustion and corrosive.

Halogenated hydrocarbons - chloroform CHCl3

High toxicity.
Low flammable hazard, give toxic products of combustion.

Aldehydes - acetaldehyde (ethanal) CH3CHO

Highly flammable (low flashpoint), high chemical reactivity, moderate toxicity.

Fruity odour.

Ketones - acetone (ethanone) CH3COCH3

Highly flammable (low flashpoint), low chemical reactivity and low toxicity.
Sweet odour.

Esters - ethyl acetate CH3COOCH2CH3

Highly flammable and non-toxic.
Pleasant odours and flavours, used in the food industry.
The reaction between acids and alcohols produces ester and water.

Amides - diethyl acetamide CH3CON(C2H5)

Hazardous chiefly because of toxic products of combustion, hydrogen cyanide.
Formed in the reaction between ammonia and organic acid.

Ethers - diethyl ether CH3CH2OCH2CH3

Highly flammable with dense heavy vapours.
May form explosive peroxides in air.
Anaesthetic.
Formed by the combination of two alcohols with the loss of water.

REACTIVITY
There are many things that affect reactivity or rate of a reaction. A bronze statue may be said to
be reactive with air and will slowly turn green but we are not unduly worried by this process as
the rate of reaction is very slow:Temperature: the rate of reaction increases with temperature, approximately double for every ten
degrees centigrade rise in temperature (see energy diagrams).
Quantity: the rate is proportional to some order of the quantity, that means the quantity squared
nd
rd
(2 order reactions) or cubed (3 order) etc.
Form: solid lumps, finely divided, liquid, gaseous or in solution form.
It is only molecules in contact with each other that are likely to react, which is most likely to
happen when substances are finely divided, in solution or in well-mixed liquid or gaseous

phases.
The presence of some other substances may be a catalyst (promoter) or inhibiter.
When you think that there are millions of molecules in one cubic centimetre it is unlikely that
any substance will be absolutely pure, and reactions are happening all the time.
One chemical bond may have to be broken before another reaction can take place. Rate of
reaction is often controlled by how strongly electrons are bound to a molecule or how strongly
they are attracted away.
As mentioned earlier, with larger organic molecules the shape of the molecule may also decide
whether a functional group is accessible to the functional groups on the attacking molecule.
pH may affect the rate of a reaction.
When a substance is in a situation where reaction is unlikely it is said to be STABLE.
It is all to do with which atoms or compounds attract or bind to their electrons the strongest,
and the amount of available energy (heat) to break chemical bonds. The purpose of one
functional group may be to make another functional group more or less negatively charged by
moving electrons through the molecule and thus more or less reactive.
Inhibitors may preferentially react with a chemical invader from outside such as water or
atmospheric oxygen which would otherwise act as a catalyst for unwanted reactions, or they may
shield reactive sites on a molecule by temporarily reacting with them.
Note therefore that even if the data sheet says that a substance may have unwanted hazardous
reactions, they may not occur unless the right conditions are provided, hence the reason for
taking careful note of any conditions of carriage. Note also that some additives may require
special conditions for them to work.e.g.availabilty of atmospheric oxygen.
AROMATIC COMPOUNDS
Cyclic Compounds
As well as forming chains and branched chains, carbon compounds can also form closed rings or
'cyclic' compounds for example cyclohexane.

(a)

(b)

Figure 10 (a) Cyclohexane and (b) short form

In the cyclohexane compound each carbon has two of its bonds to another carbon and two to a
hydrogen.
Cylcohexane is highly flammable.

The Phenyl Group

There is a special form of cyclic compound which is very important in organic and bio-chemistry
which is a ring of six carbons with each carbon being associated with only one hydrogen leaving
six electrons on the outside of the molecule free for further chemical bonding.

(a)

(b)

Figure 11 (a) Benzene and (b) its short form

Compounds can be formed by bonding functional groups to this ring or by attaching rings as
branches on chain molecules or forming chains of rings. Those compounds containing only
carbon and hydrogen are termed aromatic hydrocarbons from the Greek word aroma, meaning a
ring.
Add a methane

Figure 12 Methyl benzene (toluene)

Add another giving the three isomers of dimethyl benzene (zylene)

(a)

(b)

(c)

Figure 13 dimethyl benzene (a) ortho- (b) meta- (c) para-

Instead add an -OH to turn it into an alcohol

Figure14 Phenol
Highly flammable, toxic products of combustion, toxic if swallowed, burns skin and eyes.
Begin to make chains

Figure 15 Napthalene
These aromatic compounds are mostly flammable, have short term (acute) toxic effects, have
anaesthetic effects or long term (chronic) effects.
Repeated exposures to benzene for instance may lead to blood and bone disorders (see hazards).
Molecules based on substituted benzene chains often appear in body control chemistry as
messenger chemicals, such as hormones, which are secreted by one organ to control others. It is
this similarity to the chemicals of life which can lead to toxic effects.
Aromatic hydrocarbons in varying amounts appear in petroleum cargoes such as gasolines.
Generally closed loading is used but if tanks have to be entered that have carried such products
then checks must be carried out to ensure that safe levels are not exceeded and personal
protective equipment should be worn.

THE REACTIVE GASES

The chemical gases commonly transported in liquefied gas carriers which are considered to be
chemically reactive are inorganic compounds such as chlorine and ammonia or substituted
hydrocarbons such as vinyl chloride monomer, ethylene oxide and propylene oxide. Since
these gases do not belong to one particular family their chemical properties vary.

Liquid ammonia is a colourless alkaline liquid with a pungent odour.

It must be considered flammable although it requires a high ignition energy and is only
flammable at high concentrations (16-25%)
Ammonia is also toxic and highly reactive. It can form explosive compounds with mercury,
chlorine, iodine, bromine, calcium, silver oxide and silver hypochlorite. Ammonia vapour is
extremely soluble in water and will be absorbed rapidly and exothermically to produce a strongly
alkaline solution of ammonium hydroxide (mild heating). One volume of water will absorb
approximately 200 volumes of ammonia vapour. For this reason it is extremely undesirable to
introduce water into a tank containing ammonia vapour as this can result in a vacuum condition
rapidly developing within the tank. However water sprays may be used to remove ammonia
vapour from the air.
Ammonia is corrosive to copper alloys, aluminium alloys and galvanised surfaces because of its
alkalinity. Phenolic resins, polyvinyl chloride, polyesters and viton rubbers are not suitable for
ammonia service. Mild steel, stainless steel, neoprene rubber and polythene are, however,
suitable.
Vinyl chloride monomer (VCM) is a colourless liquid with a characteristic sweet odour. It is
highly reactive, though not with water, and may polymerise in the presence of oxygen, heat and
light. Its vapours are both toxic and flammable. Aluminium alloys, copper, silver, mercury and
magnesium are unsuitable for vinyl chloride service. Steels are, however, chemically compatible.
Ethylene oxide and propylene oxide are colourless liquids with an ether-like odour. They are
flammable, toxic, highly reactive and likely to polymerise. Both gases may react dangerously
with ammonia. Cast iron, mercury, aluminium alloys, copper and alloys of copper, silver and its
alloys, magnesium and some stainless steels are unsuitable for the handling of ethylene oxide.
Mild steel and certain other stainless steels are suitable as materials of construction for both
ethylene and propylene oxides.
Liquefied Chlorine is a yellow liquid which evolves a green vapour. It has a pungent and
irritating odour. It is highly toxic but is non-flammable though it should be noted that chlorine
can support combustion of other flammable materials in much the same way as oxygen. It is
soluble in water forming a highly corrosive acid solution and can form dangerous reactions with
all the other liquefied gases. In the moist condition, because of its corrosivity, it is difficult to
contain. Dry chlorine is compatible with mild steel, stainless steel, monel and copper. Chlorine
is very soluble in caustic soda solution which can be used to absorb chlorine vapour.
This information is given as an example of cargo properties, it does not need to be committed to
memory. Remember that a ship carrying chemical cargoes will have on board safety data sheets
for the cargo carried.
Note that ammonia may be carried on a chemical tanker as a solution in water (ammonium
hydroxide).
Polymerisation
With heat and pressure, or the use of a catalyst, single molecules (monomers) of a carbon
compound may link together to form long chains (polymers).
e.g. At 200C and 2000 bars pressure or in the presence of oxygen, ethene may polymerize to
polythene.

Figure 16 polymerisation of ethene(ethylene)

This can then be spun into fibres, moulded or extruded; cross linking the chains would make the
plastic more rigid.
There is a more complicated version of polymerisation, where for each link made a molecule of
water is produced. A list of products obtained from polymers would be solvents, textiles,
plastics, drugs, insecticides and detergents.
Polymerisation is exothermic and may have violent results if uncontrolled.
In other words, polymerisation takes place when a single molecule (a monomer) reacts with
another molecule of the same substance to form a dimer. This process can continue until a long
chain molecule is formed possibly consisting of many thousands of individual molecules.
The mechanism is illustrated for vinyl chloride monomer VCM in figure above. The process is
exothermic and may be initiated spontaneously or may be catalysed by the presence of oxygen or
impurities or by the transfer of heat to the cargo. Throughout polymerisation, the cargo becomes
more viscous until, finally, a solid polymer may be formed.
While many of the liquefied gases are theoretically polymerisable (as indicated by the presence
of a double bond in their molecular structure), difficulties in this respect only arise in practice in
the case of butadiene, isoprene, ethylene oxide and vinyl chloride monomer.

Figure 17 Polymerisation of VCM

Cargoes likely to polymerise may need chemical inhibitors to be added for safe transport. Or
some cargoes may be transported under a nitrogen blanket to exclude oxygen. A nitrogen
blanket may also be used to reduce the fire risk in flammaable liquid cargoes such as diethyl
ether. Pyrophoric cargoes such as phosphorous may be under a water blanket. (pyrophoric
means will ignite spontaneously on exposure to air.

On gas carriers carrying LPG there may be an operational problem in the formation of hydrates,
white solids, which can block filters and damage valves. Methanol may be used to inhibit this
process, but care has to be taken with polymerisable cargoes as methanol may interfere with the
1
mechanism of polymer inhibition.
Peroxide formation
Another unwanted reaction which may occur with some chemical cargoes is the formation of
peroxides. Compounds formed by the chemical combination of cargo liquid or vapour with
atmospheric oxygen, or oxygen from another source. These compounds may in some cases be
highly reactive or unstable and constitute a potential hazard.
Inhibitors or stabilisers
It should be understood that, when doing their work, chemical inhibitors may be consumed and
may need topping up, they are also often very toxic substances and need to be handled with care.
Cargoes which are liable to decompose, such as hydrogen peroxide may need chemical
2
stabilisers to be added.
Where unwanted reactions are likely, care has to be taken that that the conditions required for it
to happen during the ship's voyage are not present. Exposure to temperature rise, contact with
air, or any material which could act as a catalyst or destroy an inhibitor, has to be designed out of
the operation. Where additives have to be used the ship should be supplied with a certificate of
3
protection, an example of which (for a gas carrier) follows.
The cargo officer should ensure that a Certificate of Inhibitor Addition is received from the
shipper before departure from the loading port. This certificate should provide the following
information.

Name of inhibitor

ppm added

Date inhibitor added

Duration of protection

Recommended cargo carriage temperature

ppm required for effective inhibition

Toxic properties of inhibitors

If a cargo has to be inhibited for transport, an inhibitor certificate must be issued from the
terminal or shipper prior to departure. (Paragraph 17.8 of IGC Code)
The following is an inhibitor certificate.

LIQUEFIED GAS - INHIBITOR INFORMATION FORM

To be completed before loading an inhibited cargo
SHIP.......................................

DATE..........................

PORT&BERTH.................................

TIME..........................

1. CORRECT TECHNICAL NAME OF CARGO...........................................

2. CORRECT TECHNICAL NAME OF
INHIBITOR.................................................................
3. AMOUNT OF INHIBITOR ADDED.................................................
4. DATE ADDED................................................................
5. EXPECTED LIFETIME OF INHIBITOR............................................
6. ANY TEMPERATURE LIMITATIONS
AFFECTING INHIBITOR......................................................
7. ACTION TO BE TAKEN IF VOYAGE
EXCEEDS EFFECTIVE LIFETIME OF
INHIBITOR.................................................................
IF ABOVE INFORMATION NOT SUPPLIED, CARGO SHOULD BE REFUSED
(IMCO Codes 18.1.2)
FOR SHIP.........................
(SIGNED)

FOR SHORE...............................
(SIGNED)

There are no inhibitors for some reactive cargoes.

These cargoes will have to be transported under positive pressure of inert gas with an oxygen
concentration of 0.2% or less by volume (see Paragraph 17.6 of IGC Code).
The cargoes in chemical tankers are liquids having a vapour pressure not exceeding 2.8 bar
absolute at a temperature of 37.8C (see Paragraph 1.1.2 of IBC Code).

Additional information for liquid cargoes would be whether the additive is oxygen dependent.
Cargo interests and in some cases recommendations may require the presence of an expert to
ensure that correct amounts of an additive have been applied.
The International Chamber of Shipping has a collection of Safety Data Sheets for various
chemical cargoes and the United States Coastguard publishes safety data sheets and
compatability data as well as an emergency response database called CHRIS. This can be
accessed at their website www.chrismanual.com
Figure The US Coastgaurd Compatability Data
Figure The US Coastguard Safety Data Sheet for Phenol
Under the US Coastguard DOT rules for testing for incompatability, chemicals are considered
incompatable if there is a violent hazardous reaction or if in the test conditions there is a rise in

temperature of more than 25 C or gases are evolved.

There also has to be compatability for materials of construction, tank linings, gaskets etc. and
advice for personnel protective equipment for safety of the crew and jetty staff. The codes also
include information for protection of the environment.
References
1. Liquefied Gas Handling Principles on Ships and in Terminals, McGuire and
White, Witherby
2. International Code for the Construction and Equipment of Ships
Carrying Dangerous Chemicals in Bulk (IBC Code) IMO 1994
3. International Code for the Construction and Equipment of Ships
Carrying Liquefied Gases in Bulk (IGC Code) IMO 1993
4. International Maritime Dangerous Goods Code IMO.

IGC Code - Paragraph 17.6

Page 1 of 1

17.6 Exclusion of air from vapour spaces

Air should be removed from the cargo tanks and associated piping before loading and then
subsequently excluded by:
1. introducing inert gas to maintain a positive pressure. Storage or production capacity of the
inert gas should be sufficient to meet normal operating requirements and relief valve leakage.
The oxygen content of inert gas should at no time be greater than 0.2% by volume; or
2. control of cargo temperatures such that a positive pressure is maintained at all times.

IGC Code - Paragraph 17.8

Page 1 of 1

17.8 Inhibition
Care should be taken to ensure that the cargo is sufficiently inhibited to prevent polymerization at all
times during the voyage. Ships should be provided with a certificate from the manufacturer stating:
1.
2.
3.
4.

name and amount of inhibitor added;

date inhibitor was added and the normally expected duration of its effectiveness;
any temperature limitations affecting the inhibitor;
the action to be taken should the length of the voyage exceed the effective lifetime of the
inhibitors.

IBC Code - 1.1.2

Page 1 of 1

1.1.2
Liquids covered by the Code are those having a vapour pressure not exceeding 2.8 bar absolute at a
temperature of 37.8C.